Structure of five molecular salts assembled from noncovalent associations between organic acids, imidazole, benzimidazole, and 1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole

Accepted Manuscript Structure of five molecular salts assembled from noncovalent associations between organic acids, imidazole, benzimidazole, and 1-(2-(1H-benzimidazol-1-yl)ethyl)-1Hbenzimidazole Xuchong Chen, Shouwen Jin, Huan Zhang, Xiao Xiao, Bin Liu, Daqi Wang PII:

S0022-2860(17)30624-5

DOI:

10.1016/j.molstruc.2017.05.041

Reference:

MOLSTR 23782

To appear in:

Journal of Molecular Structure

Received Date: 8 December 2016 Revised Date:

10 May 2017

Accepted Date: 10 May 2017

Please cite this article as: X. Chen, S. Jin, H. Zhang, X. Xiao, B. Liu, D. Wang, Structure of five molecular salts assembled from noncovalent associations between organic acids, imidazole, benzimidazole, and 1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.05.041. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Graphical Abstracts

Title: Structure of Five Molecular Salts Assembled from Noncovalent Associations

between

Organic

Acids,

Imidazole,

Benzimidazole,

and

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1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole

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Xuchong Chena, ShouwenJina,b*, Huan Zhanga,b*, Xiao Xiaoa,b, Bin Liua,b, and Daqi Wangc

ZheJiang A & F University, Lin’an, Zhejiang Province, 311300, P. R. China. *E-mail:

[email protected] b

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a

Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province

Zhejiang A & F University, Lin’an, Zhejiang Province, 311300, P. R. China

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Department of Chemistry, Liaocheng University, Liaocheng 252059, P. R. China.

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c

ACCEPTED MANUSCRIPT Structure of Five Molecular Salts Assembled from Noncovalent Associations between

Organic

Acids,

Imidazole,

Benzimidazole,

and

1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole Xuchong Chena, ShouwenJina,b*, Huan Zhanga,b*, Xiao Xiaoa,b, Bin Liua,b, and Daqi

a

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Wangc ZheJiang A & F University, Lin’an, Zhejiang Province, 311300, P. R. China. *E-mail:

[email protected] b

Key Laboratory of Chemical Utilization of Forestry Biomass of Zhejiang Province

Department of Chemistry, Liaocheng University, Liaocheng 252059, P. R. China.

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c

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Zhejiang A & F University, Lin’an, Zhejiang Province, 311300, P. R. China

Abstract:

Cocrystallization of the imidazole derivatives, L1-L3, with a series of organic acids gave a total of five molecular salts with the compositions: (imidazole) : (DL-10-camphorsulfonic acid) [(HL1+) · (cpsa-), cpsa- = DL-10-camphorsulfonate]

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(1), (imidazole) : (3,5-dihydroxybenzoic acid) [(HL1+) · (3,5-dba-), 3,5-dba- = 3,5-dihydroxybenzoate]

(2),

(imidazole)

:

(isophthalic

acid)

:

H2O

[(HL1)+ · (Hmpa)- · H2O, Hmpa- = hydrogenisophthalate] (3), (benzimidazole) :

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(butane-1,2,3,4-tetracarboxylic acid) [(HL2+) · (H3bta -), H3bta- = trihydrogen butane-1,2,3,4-tetracarboxylate]

(4),

and

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1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole :

(benzimidazole)2

:

(5-nitrosalicylic acid)2

[(L2)2 · (H2L3)2+ · (5-nsa-)2, 5-nsa- = 5-nitrosalicylate], (5). The five salts have been characterised by XRD technique, IR, and EA, and the melting points of all the salts were also reported. And their structural and supramolecular aspects are fully analyzed. The result reveals that among the five investigated crystals the ring N in the imidazole moieties are protonated when the organic acids are ionized, and the crystal packing is interpreted in terms of the strong N-H O H-bond from the imidazole and the ionized acids. In addition to the N-H O H-bond, the O-H···O H-bonds were also

ACCEPTED MANUSCRIPT established at the salts 2-5, compound 1 has the additional N-H···S H-bonds. Further analysis of the crystal packing of the salts displayed that a different family of additional CH-O/CH2-O/CH3-O, CH-S, CH-π, NH-π, and π-π associations contribute to the stabilization and expansion of the total 3D framework structures. For the

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coexistence of the various weak interactions these structures had homo or hetero supramolecular synthons or both. Some classical supramolecular synthons, such as R12(4), R22(7), and R22(8) usually observed in crystals of organic acids with imidazole, were again shown to be involved in constructing most of these hydrogen bonding

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networks.

Acidic components; Organic salts.

Introduction

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Keywords: Crystal structures; Noncovalent associations; Imidazole derivatives;

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Noncovalent interactions such as electrostatic forces, H-bond, CH-π, π-π stacking, cation-π, anion-π, and lone pair-π contacts, as well as other weak bonds play key roles in molecular recognition, host-guest chemistry, crystal engineering, supramolecular

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chemistry, biochemistry, pharmaceutical chemistry, and materials science [1-4]. In the past few years, great efforts have been made to elucidate these interactions and their relationship to the final supramolecular structures [5], but it is still remained a

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difficult task to build ordered solid-state materials via a predictable manner. The study of a wide variety of delicate non-covalent interactions has currently led to the foundation of the supramolecular synthon approach in the supramolecular syntheses. The supramolecular synthons are the basic structural units within organic solids produced by the intermolecular interactions, and they can be categorized into supramolecular homo- and heterosynthons, which are the most successful strategy for the chemist to understand and design the organic salt/cocrystal. With respect to pharmaceutical ingredients, solid organic salts with such biopharmaceutical properties as solubility, stability and hygroscopicity have been

ACCEPTED MANUSCRIPT studied systematically, and these properties are relevant to the noncovalent interactions [6-7]. The organic acids with the nice donor-acceptor groups are excellent blocks for the multi-component assembly [8], and they aggregate in the solid state as dimer, catemer, and bridged motifs [9], so they are frequently used as building blocks

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in the supramolecular crystal engineering. A myriad of acid-base mediated supramolecular assemblies were developed through the powerful and directional recognition between the organic acids, the aromatic amine, aliphatic amine and pyridyl derivatives [10, 11]. In order to create

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high-dimensional assemblies and elucidate molecular crystals between the imidazole units and the organic acids, we select some organic acids possessing CH3, CH2, C=O,

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NO2, CH, OH, and aromatic moieties which are all common groups in creating the organic crystalline solids by forming a wide variety of non-covalent interactions [12]. Imidazole group as an important hetero-aromatic moiety appeared in many pharmaceutical formula. In addition, imidazole derivatives as one of the most common N-heterocyclic compounds have been said to be the best acceptor for the

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carboxylic acids in the supramolecular salt syntheses. Except the basic ring N, L1-L3 has the additional rigid aryl ring and the somewhat flexible CH2 bridges at L3, which can generate more intricate noncovalent associations when it associated with the

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organic acids. To the best of our knowledge there are a few reports dealing with the imidazole/benzimidaole, sulfonic acid, dihydroxybenzoic acid, isophthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-benzene-tetra-carboxylic acid, and

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5-nitrosalicylic acid adducts concerning the L1-L3 [13, 14]. Recently, we have focused our continuing efforts on the systematic study of

H-bond (HB), π-π stacking, and halogen bond (XB) from the given N-containing derivatives with varying the organic acids [15], in this contribution we will report herein the preparation and structures of five organic salts assembled from imidazole derivatives (L1-L3) and the corresponding organic acids ranging from mono-acid to tetra-acid (Scheme 1), respectively. The five organic salts are (imidazole) : (DL-10-camphorsulfonic acid) [(HL1+) · (cpsa-), cpsa- = DL-10-camphorsulfonate] (1), (imidazole) : (3,5-dihydroxybenzoic acid) [(HL1+) · (3,5-dba-), 3,5-dba- =

ACCEPTED MANUSCRIPT 3,5-dihydroxybenzoate]

(2),

(imidazole)

:

(isophthalic

acid)

:

H2O

[(HL1)+ · (Hmpa)- · H2O, Hmpa- = hydrogenisophthalate] (3), (benzimidazole) : (butane-1,2,3,4-tetracarboxylic acid) [(HL2+) · (H3bta-), H3bta- = trihydrogen butane-1,2,3,4-tetracarboxylate]

(4),

and

(benzimidazole)2

(5-nitrosalicylic acid)2

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1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole :

:

[(L2)2 · (H2L3)2+ · (5-nsa-)2, 5-nsa- = 5-nitrosalicylate], (5) (Scheme 2). The supramolecular synthons of the salts 1-5 were listed at Scheme 3. The major goal of the manuscript is to take a systematic structural investigation on the organic salts of

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imidazole derivatives and elucidate the underlying supramolecular synthons, thus develop new building blocks for the supramolecular chemistry of imidazole

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derivatives. OH

HO

O

HO

S O

OH

O

O

OH

3,5-dihydroxybenzoic acid

O

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DL-10-camphorsulfonic acid

HO

O m-Phthalic acid

HO

OH

O

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O

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H N

HO

butane-1,2,3,4-tetracarboxylic acid

H N

O

OH

O

HO

OH

NO2 N

O 5-nitrosalicylic acid

N N N

N

L2

N

L3

Scheme 1 The building blocks utilized in this manuscript.

L1

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Scheme 2 The five salts described in this paper, 1-5.

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Scheme The synthons at the salts 1-5.

Experimental Section Materials and Methods The chemicals and solvents used in this work were of analytical grade commercial products and were used without further purification. The FT-IR spectra were recorded from KBr pellets in range 4000-400 cm-1 on a Mattson Alpha-Centauri

ACCEPTED MANUSCRIPT spectrometer equipped with DTGS detector operating with scan's numbers of 64 and resolution of 4 cm-1, and the IR bands were marked as strong (s), medium (m), and weak (w) at the preparation part. The asymmetrical and symmetrical IR vibration bands of the corresponding groups were shown as νas and νs, respectively. The C, H, N,

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and S data were obtained microanalytically on a Perkin-Elmer elemental analyzer with Model 2400II, and the melting points of the new compounds were measured by an XT-4 thermal apparatus without correction.

Salts 1-5 were prepared by the same method of mixing the acids with the

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imidazole derivatives at 1:1 ratio in CH3OH/CH3CH2OH solvents, and the crystals were obtained at ambient conditions via the common solvent evaporating technique.

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All compounds crystallized without H2O or CH3OH/CH3CH2OH molecules except 3, and the five crystalline salts are not hygroscopic.

Preparation of the salts

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a. (imidazole) : (DL-10-camphorsulfonic acid) [(HL1+) · (cpsa-), cpsa- = DL-10-camphorsulfonate] (1)

A solution of DL-10-camphorsulfonic acid (23.2 mg, 0.10 mmol) in 8 mL methanol was added dropwise to a vigorously stirred solution of imidazole L1 (6.8

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mg, 0.1 mmol) in ethanol (2 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left

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standing at room temperature for 10 days, colorless block crystals were isolated after slow evaporation of the solution in air. The crystals were collected and dried in air to give the title compound [(HL1+) · (cpsa-)] (1). (yield: 26 mg, 86.56%). mp 146-148°C. Elemental analysis: Calc. for C13H20N2O4S (300.37): C, 51.94; H, 6.66; N, 9.32; S, 10.65. Found: C, 51.82; H, 6.54; N, 9.20; S, 10.54. Infrared spectrum (KBr disc, cm-1): 3422s(νas(NH)), 3387s(νs(NH)), 3135m, 3087m, 2966m, 1731m, 1622m, 1575m, 1528m, 1476m, 1433m, 1389m, 1356m, 1311m, 1266m, 1221m, 1180m, 1142m, 1100m, 1056m, 1013m, 969m, 925m, 881m, 837m, 794m, 749m, 708m, 666m, 629m, 604m.

ACCEPTED MANUSCRIPT b. (imidazole) : (3,5-dihydroxybenzoic acid) [(HL1+) · (3,5-dba-), 3,5-dba- = 3,5-dihydroxybenzoate] (2) A solution of 3,5-dihydroxybenzoic acid (15.0 mg, 0.10 mmol) in 10 mL ethanol was added dropwise to a vigorously stirred solution of imidazole L1 (6.8 mg, 0.1

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mmol) in ethanol (2 ml) over a period of 5 min. The solution was stirred for a few minutes, then the solution was filtered into a test tube. The solution was left standing at room temperature for 15 days, colorless block crystals were isolated after slow evaporation of the solution in air. The crystals were collected and dried in air to give

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the title compound [(HL1+) · (3,5-dba-)] (2). (yield: 15 mg, 67.51%). mp 160-161°C. Elemental analysis: Calc. for C10H10N2O4 (222.20): C, 54.01; H, 4.50; N, 12.60.

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Found: C, 53.95; H, 4.39; N, 12.48. Infrared spectrum (KBr disc, cm-1): 3682s(br, ν(OH)), 3443s(νas(NH)), 3333s(νs(NH)), 3240m, 3144m, 3064m, 2990m, 2914m, 1606s(νas(COO-)), 1563m, 1514m, 1470m, 1437m, 1400s(νs(COO-)), 1357m, 1313m, 1270m, 1225m, 1177m, 1132m, 1089m, 1043m, 1001m, 949m, 898m, 856m, 815m,

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772m, 731m, 688m, 647m, 621m, 600m.

c. (imidazole) : (isophthalic acid) : H2O [(HL1)+ · (Hmpa)- · H2O, Hmpa- = hydrogenisophthalate] (3)

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A solution of isophthalic acid (16.6 mg, 0.1 mmol) in 10 mL methanol was added dropwise to a vigorously stirred solution of imidazole L1 (6.8 mg, 0.1 mmol) in ethanol (2 ml) over a period of 5 min. The solution was stirred for a few minutes, then

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the solution was filtered into a test tube. The solution was left standing at room temperature for 20 days, colorless block crystals were isolated after slow evaporation of the solution in air. The crystals were collected and dried in air to give the title compound [(HL1)+ · (Hmpa)- · H2O] (3). (yield: 19 mg, 75.33%). mp 212-213°C. Elemental analysis: Calc. for C11H12N2O5 (252.23): C, 52.33; H, 4.76; N, 11.10. Found: C, 52.22; H, 4.64; N, 11.02. Infrared spectrum (KBr disc, cm-1): 3701s(ν(OH)), 3458s(multiple, νas(NH)), 3378s(νs(NH)), 3122m, 3085m, 2980m, 2861m, 2790m, 1651s(ν(C=O)), 1600m, 1575s(νas(COO-)), 1534m, 1489m, 1442w, 1380s(νs(COO-)), 1336m, 1290s(ν(C-O)), 1242m, 1199m, 1157m, 1114m, 1070m, 1028w, 979m, 933m,

ACCEPTED MANUSCRIPT 884m, 839m, 786m, 742m, 699m, 656m, 628m, 611w.

d. (benzimidazole) : (butane-1,2,3,4-tetracarboxylic acid) [(HL2+) · (H3bta -), H3bta- = trihydrogen butane-1,2,3,4-tetracarboxylate] (4)

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A solution of butane-1,2,3,4-tetracarboxylic acid (23.4 mg, 0.1 mmol) in methanol (16 ml) was added dropwise to a vigorously stirred solution of benzimidazole L2 (11.8 mg, 0.1 mmol) in methanol (8 ml) over a period of 5 min. The solution was stirred for a few minutes, filtered into a test tube, and left standing at

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room temperature for 26 days. Colorless block crystals were isolated after slow evaporation of the CH3OH solution in air. The crystals were collected and dried in air

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to give the title compound [(HL2+) · (H3bta-)] (4). (yield: 30 mg, 85.15%). mp 202-203°C. Elemental analysis: Calc. for C15H16N2O8 (352.30): C, 51.09; H, 4.54; N, 7.95. Found: C, 51.02; H, 4.45; N, 7.82. Infrared spectrum (cm-1): 3658s(ν(OH)), 3445s(multiple, νas(NH)), 3350s(νs(NH)), 3144m, 3080m, 2992m, 2925m, 2834m, 1730s(ν(C=O)), 1672m, 1629m, 1587s(νas(COO-)), 1545m, 1507m, 1469m, 1426m,

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1379s(νs(COO-)), 1332m, 1289s(ν(C-O)), 1245m, 1203m, 1159m, 1116m, 1069m, 1022m, 979m, 934m, 890m, 843m, 802m, 759m, 714m, 668m, 636m, 615m.

e. (benzimidazole)2 : 1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole :

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(5-nitrosalicylic acid)2 [(L2)2 · (H2L3)2+ · (5-nsa-)2, 5-nsa- = 5-nitrosalicylate], (5) A solution of 5-nitrosalicylic acid (36.6 mg, 0.2 mmol) in 8 mL methanol was dropwise

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added

to

a

vigorously

stirred

solution

of

1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole L3 (28 mg, 0.10 mmol), and benzimidazole L2 (11.8 mg, 0.1 mmol) in 18 mL of methanol over a period of 5 min. The solution was stirred for a few minutes, filtered into a test tube, and left standing at room temperature for one month. Colorless block crystals were isolated after slow evaporation of the CH3OH solution in air. The crystals were collected and dried in air to give the title compound [(L2)2 · (H2L3)2+ · (5-nsa-)2] (5). (yield: 72 mg, 83.25%, based on 5-nitrosalicylic acid). mp 192-193°C. Elemental analysis: Calc. for C44H36N10O10 (864.83): C, 61.05; H, 4.16; N, 16.19. Found: C, 60.93; H, 4.06; N,

ACCEPTED MANUSCRIPT 16.08.

Infrared

3360s(νs(NH)),

spectrum 3140m,

(cm-1):

3069m,

3679s(ν(OH)),

2990m,

1770w,

3455s(multiple, 1609s(νas(COO-)),

νas(NH)), 1562m,

1526s(νas(NO2)), 1480w, 1434m, 1389s(νs(COO-)), 1345m, 1318s(νs(NO2)), 1269m, 1225m, 1176m, 1129m, 1080m, 1036m, 989m, 947m, 902m, 857m, 814m, 767m,

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727m, 684m, 650m, 624m, 600m.

X-ray Crystallography

Single-crystal X-ray diffraction studies for the five compounds were performed

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via a Bruker SMART 1000 CCD diffractometer operating at 50 kV and 40 mA using Mo Kα radiation (λ = 0.71073 Å, monochromator graphite). Data collection and

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reduction were completed using the SMART and SAINT softwares [16], and the structures were solved by direct methods, and the non-H atoms were subjected to anisotropic refinement by full-matrix least squares on F2 using SHELXTL package [17].

All Hs were placed in geometrically calculated positions and included in the

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refinement in a riding-model approximation. Data collection and structure refinement parameters along with crystallographic data for all salts are given in Table 1, while selected bond lengths, bond angles, and H-bond geometries are listed in Tables 2, and

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3.

Table 1 should be inserted here

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Table 2 should be inserted here

Table 3. should be inserted here

Results and Discussion

X-ray structure analysis of 1-5 X-ray structure of (imidazole) : (DL-10-camphorsulfonic acid) [(HL1+) · (cpsa-), cpsa- = DL-10-camphorsulfonate] (1) Fig. 1 should be inserted here

ACCEPTED MANUSCRIPT Fig. 2 should be inserted here The analysis of the XRD data indicated the title compound crystallized as monoclinic colorless crystals in the space group P2(1). Fig. 1 shows the asymmetric unit

of

the

compound

1

that

contains

two

imidazoliums,

and

two

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DL-10-camphorsulfonates. Similar with the published salt of zolmitriptan camphorsulfonate [18], the SO3H of the DL-10-camphorsulfonic acid gets fully dissociated and the ring N of the L1 is protonated. The N-H position is unambiguously identified through the difference electron density map. The S-O bonds

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covered the range from 1.429(9) Å - 1.459(6) Å, the C-O bonds (1.185(14) Å, and 1.265(15) Å) at the anion are for the typical keto groups, and all these bond lengths

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were similar to the corresponding bonds at the salt of zolmitriptan camphorsulfonate [18].

One HL1 was bonded to one DL-10-camphorsulfonate by the N-H···O H-bond between the NH+ and the SO3- with N-O distance of 3.002(12) Å, bifurcated CH-O associations between the N-CH-N of the HL1 and two O from the SO3- with C-O

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distances of 3.056-3.417 Å, and CH-S association between the N-CH-N of the HL1 and the S of the SO3- with C-S separation of 3.770 Å to form a heteroadduct A. The other HL1 was bonded to the other DL-10-camphorsulfonate by the N-H···O H-bond between the NH and one O of the SO3- with N-O distance of 2.747(10) Å, N-H···S

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H-bond between the NH and the S of the SO3- with N-S distance of 3.806(8) Å, and CH-O association between the ring CH of the HL1 and the C=O at the anion with

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C-O distance of 3.087 Å to form a heteroadduct B. The heteroadduct A and the heteroadduct B produced a tetracomponent aggregate AB by the CH-O association from CH of the HL1 at the heteroadduct B and the O of the SO3- in the heteroadduct A that was involved in the CH-O association with C-O distance of 3.066 Å. The tetracomponent aggregates AB were linked into 1D chain running along the c axis with the assistance of the N-H···O H-bond between the NH of the heteroadduct A and the second O of the SO3- at the heteroadduct B with N-O distance of 2.855(13) Å, and CH-O associations from CH of the HL1 at the heteroadduct A and the O of the SO3in the heteroadduct B that was involved in the N-H···O H-bond with C-O distance of

ACCEPTED MANUSCRIPT 3.348 Å. Within the crystal structure, neighboring chains are linked through additional interchain N-H···O H-bonds between the NH and the SO3- with N-O distances of 2.793(11)-3.082(13) Å, and N-H···S H-bond between the NH and the SO3- with N-S

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distance of 3.828(10) Å to give a 2D corrugated sheet extending parallel to the bc plane (Fig. 2). In addition, the crystal lattice is stabilized further through interchain CH-O associations between the ring CH of the HL1 and the C=O at the DL-10-camphorsulfonate with C-O distance of 3.339 Å, and between the N-CH-N of

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the HL1 and the SO3- with C-O distances of 3.092-3.344 Å. In this case the corresponding components at the neighboring chains were antiparallel to each other.

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While the corresponding components at the first chain were parallel to the corresponding components at the third chain, so did the corresponding components at the second chain and the fourth chain. The 2D sheet exhibited the I R12(4), II R21(5), III R22(4), IV R22(7), V R22(10), VI R12(7), VII R33(9), and VIII R42(10) synthons. Along the a axis, the 2D corrugated sheets were interlinked through CH3-O

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association between the CH3 of the DL-10-camphorsulfonate and the SO3- with C-O distance of 3.515 Å to form the final 3-D layer network where the neighboring sheets were glided some distance from each other along the extending directions.

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X-ray structure of (imidazole) : (3,5-dihydroxybenzoic acid) [(HL1+) · (3,5-dba-),

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3,5-dba- = 3,5-dihydroxybenzoate] (2) Fig. 3 should be inserted here Fig. 4 should be inserted here

Salt 2 crystallized as orthorhombic block crystals in the spacegroup Pna2(1), in

the asymmetric unit there contains one HL1, and one 3,5-dihydroxybenzoate (Fig. 3), and the composition was similar to the benzimidazolium 3,5-dihydroxybenzoate [19]. The C-O bonds (1.248(4) Å for O(1)-C(4), and 1.253(4) Å for O(2)-C(4)) in the COO- are almost equal to each other within the experimental error, and the C-O bond lengths (O(3)-C(7), 1.364(4) Å; and O(4)-C(9), 1.358(3) Å) of the phenol groups are agreement with the values in the unionized phenol [20]. As anticipated, the imidazole

ACCEPTED MANUSCRIPT moiety is planar with the r.m.s deviation of the imidazole ring from the mean plane of the ring being 0.0031 Å. The r.m.s deviation of the aryl ring of the 3,5-dihydroxybenzoate from the mean plane of the ring is 0.0083 Å, the plane defined by the carboxylate C4-O1-O2 twisted by 133.9° from the aryl ring of the

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3,5-dihydroxybenzoate. The plane of the aryl ring formed the dihedral angle of 66.9º with the imidazole ring. The two phenol groups at the anion adopt a syn-syn arrangement with respect to the para-H in the 3,5-dihydroxybenzoate, differing from the known adduct containing 3,5-dihydroxybenzoate [21].

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One HL1 was bonded to one 3,5-dihydroxybenzoate by the N-H···O H-bond between the NH of HL1 and the COO- with N-O distance of 2.794(4) Å, and the

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NH-π association between the NH of HL1 and the phenyl ring of the 3,5-dihydroxybenzoate with N-Cg separation of 3.325 Å to form a bicomponent heteroadduct, and in this case the N-Cg separation is in the range of the documented values [22]. Two bicomponent heteroadducts produce a tetracomponent aggregate through the O-H···O H-bond between the phenol and the COO- with O-O distance of

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2.660(3) Å, and CH-O association from the para-H of the 3,5-dihydroxybenzoate and the same O of the COO- that has the O-H···O H-bond with C-O distance of 3.349 Å. There found the IX R21(6) loop between the two bicomponent heteroadducts. Salt 2 exhibited 1-D chain based on the interlinked tetracomponent aggregates via

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the N-H···O H-bond between the NH of HL1 and the COO- with N-O distance of 2.758(4) Å. Furthermore the N-H···O H-bond between the NH of the HL1 and the

AC C

COO- with N-O distance of 2.758(4) Å, O-H···O H-bond between the phenol and the COO- with O-O distance of 2.660(3) Å, and CH-O association from the para-H of the 3,5-dihydroxybenzoate and the same O of the COO- that has the O-H···O H-bond with C-O distance of 3.349 Å connected the neighboring 1D chains into 2D grid sheet along the bc plane (Fig. 4). In the a axis direction, the 2D grid sheets were interlinked through O-H···O H-bond between the phenol and the COO- with O-O distance of 2.661(3) Å, CH-O association between the N-CH-N of the HL1 and the phenol with C-O distance of 3.196 Å, CH-O association between the CH of the HL1 and the phenol with C-O

ACCEPTED MANUSCRIPT distance of 3.330 Å, and π-π association between the imidazole ring and the aryl ring of the 3,5-dihydroxybenzoate with Cg-Cg distance of 3.322 Å to form 3D network structure.

Hmpa- = hydrogenisophthalate] (3) Fig. 5 should be inserted here Fig. 6 should be inserted here

RI PT

X-ray structure of (imidazole) : (isophthalic acid) : H2O [(HL1)+ · (Hmpa)- · H2O,

SC

As depicted in Fig. 5, the molecular structure of 3 which belongs to the orthorhombic P2(1)2(1)2(1) space group, crystallizes with one HL1, one

M AN U

m-hydrogenphthalate, and one H2O. In the compound 3 only one H of the isophthalic acid was transferred to the ring N of the L1, so 3 is a hydrogenphthalate salt. The H5B was disordered over the site of H5D, and both have the occupancy factor of 0.5. The C-O bonds in the COOH are 1.208(4) Å (O(4)-C(5)), and 1.314(5) Å (O(3)-C(5)) showing characteristic C=O, and C-O bond lengths which are also supporting the reliability of adding Hs experimentally by different electron density

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onto O. The C-O bond lengths at the COO- are ranging from 1.225(4) (O(1)-C(4)) to 1.262(4) Å (O(2)-C(4)) with the average value of 1.244(4) Å, which is longer than the C=O and shorter than the C-O in the COOH, telling that this COOH is deprotonated.

EP

The respective rms deviations of the rings with N1-N2-C1-C3, and C6-C11 are 0.0025 Å, and 0.0036 Å, and both rings inclined at an angle of 44.8° with each other.

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The carboxylates O1-C4-O2, and O3-C5-O4 twisted from the plane of the ring bearing C6-C11 by 18.3°, and 16.2°, respectively, and they made dihedral angle of 15.1° with each other, the COO- in the hydrogenphthalate was almost coplanar with the phenyl ring which is similar to the reported adduct of phthalate [23]. The N-H···O H-bond between one O of the COO- and the NH with N-O distance of 2.672(4) Å united one anion and one cation into a bicomponent adduct, and at the bicomponent adduct there was attached a H2O via the O-H···O H-bond from the same O of the COO- with O-O distance of 2.803(8) Å, generating a tricomponent adduct. The tricomponent adducts were further mediated by the CH-O association between

ACCEPTED MANUSCRIPT the CH of the HL1 and the C=O of the COOH with C-O distance of 3.163 Å to form 1D chain. There were independent CH-O associations between the CH of the HL1 and the C=O of the COOH at the anion with C-O distance of 3.218 Å, which joined the 1D chains into 2D sheet extending parallel to the ab plane (Fig. 6). With the help of

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the O-H···O H-bond between the H2O molecules with O-O distance of 2.312(5) Å, and CH-O association between the CH of the HL1 and the H2O with C-O distance of 3.249 Å, two 2D sheets were joined together to form a double sheet where the chains at the different sheets of the double sheet made an angle of ca. 60° with each other.

SC

Along the c axis, the double sheets were propagated further through the independent N-H···O H-bond between one O of the COO- and the NH with N-O distance of

M AN U

2.780(4) Å, O-H···O H-bond between the COOH and COO- with O-O distance of 2.554(3) Å, giving a 3D layer network structure. Here the COOH···COO- H-bond adopted the syn-syn conformation instead of the less common anti-anti conformation [24]. The CH-O associations between the N-CH-N of the HL1 and the OH of the COOH with C-O distances of 3.154-3.281 Å, and CH-π association between the

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N-CH-N of the HL1 and the phenyl ring of the anion with C-Cg separation of 3.507 Å between the neighboring double sheets consolidated the 3D structure. At the 3D

EP

network there established the X R32(9), XI R33(9), and XII R42(9) loops.

X-ray structure of (benzimidazole) : (butane-1,2,3,4-tetracarboxylic acid)

AC C

[(HL2+) · (H3bta-), H3bta- = trihydrogen butane-1,2,3,4-tetracarboxylate] (4)

Crystallization

Fig. 7 should be inserted here Fig. 8 should be inserted here

of

an

equal

molar

of

benzimidazole

and

butane-1,2,3,4-tetracarboxylic acid gave single crystals 4 with monoclinic space group P2/n. The compound is also a salt with one HL2, and two halves of H3btamonoanion in the asymmetric unit (Fig. 7). The H2 and H2A attached to the O2 and O2A both have occupancies of 0.5, and the H3 and H3B at the O3 and O3A both have occupancies of 1. The carboxyl groups with C5 and C8 are gauche with the torsion angle

ACCEPTED MANUSCRIPT C8-C7-C6-C5 (-55.78(3)°) larger than the corresponding angle (-48.6(3)°) in the cocrystal from 4,4’-bipyridine and butane-1,2,3,4-tetracarboxylic acid [25]. These groups are mutually twisted with the interplanar angle (89.7(2)°) between the respective planes defined by the O1, O2, C5, and C6 atoms and O3, O4, C8, and C7

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atoms larger than that [73.7(1)°] in 4,4’-bipyridine-butane-1,2,3,4-tetracarboxylic acid [25]. There documented few organic adducts from butane-1,2,3,4-tetracarboxylic acid including its hexamethylenetetraminium [26], 2-aminopyrimidinium [27], ammonium [28], and guanidinium salts [29]. Unlike 4, in the last three salts the anions are

SC

centrosymmetric, however, the conformation of the anion was similar with that found in this manuscript with the torsion angle (-55.78(3)°) close to the angles -59.62(3)° 53.62(2)°

in

the hexamethylenetetraminium

trihydrogen

1,2,3,4-butane

M AN U

and

tetracarboxylate [26], and -55.2(2)° and -60.9(2)° for the two symmetry independent anions in the ammonium salt [28].

One HL2+ and one H3bta- were held together to form a bicomponent adduct via the N(1)-H(1)···O(1)#5 (2.768(2) Å, 174.5°, #5 x+1, y+1, z) H-bond. The

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bicomponent adducts were linked together by the O-H···O H-bond between the carboxylate groups with O-O distance of 2.439(3) Å to form 1D chain running along the b axis direction, together with the CH-O associations between the aromatic CH of

EP

the HL2 and the COO- with C-O distances of 3.294-3.603 Å. The 1D chains were combined into 2D sheet extending at the direction that made an angle of ca. 60° with the bc plane (Fig. 8) by combination of the N-H···O H-bond, and CH-O association.

AC C

At the sheet there were XIII R22(11), XIV R32(10), and XV R44(21) rings. Under the O-H···O H-bond, CH-O, and CH2-O associations, the 2D sheets were brought into 3D network structure. Here the O-H···O H-bond existed between the COOH groups with O-O distance of 2.6280(18) Å. The CH-O associations were established between the N-CH-N of the HL2 and the carboxyl with C-O distance of 3.249 Å, and between the CH of the anion and the carboxyl with C-O distance of 3.536 Å. The CH2-O association was between the CH2 spacer of the H3bta- and the carboxyl with C-O distance of 3.561 Å. For these associations there generated the intersheet XVI R21(6), XVII R22(8), and XVIII R22(8) loops.

ACCEPTED MANUSCRIPT X-ray

structure

of

(benzimidazole)2

1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole :

:

(5-nitrosalicylic acid)2

[(L2)2 · (H2L3)2+ · (5-nsa-)2, 5-nsa- = 5-nitrosalicylate], (5) Fig. 9 should be inserted here Fig. 10 should be inserted here

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Compound 5 is a 2 : 1 : 2 salt composed of one L2, half a dication of H2L3, and one 5-nitrosalicylate (Fig. 9), and the composition of 5 was different from the reported salt of 5-sulfosalicylic acid [30]. Compound 5 crystallized in the triclinic

SC

P-1 spacegroup, there is one unit in the unit cell. The C(1) and C(1A) and the attached H atoms to C(1) and C(1A) were all disordered over two sites with equal occupancies,

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respectively. The C-O bonds of the COO- ranged from 1.248(5) Å (O(1)-C(16)) to 1.268(5) Å (O(2)-C(16)) with ∆ = 0.020 Å, which suggests that the COOH is deprotonated. The phenol moiety remains protonized as evidenced by the C18-O3 bond (1.333(5) Å), and the H2L3 displays trans conformation.

For the intramolecular H-bond (O(3)-H(3A)···O(2), 2.470(4) Å, 148.8°) from the

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COO- and the phenol, it is found that the COO- is approximately coplanar with the aryl ring with the torsion angle C18-C17-C16-O1 being 176.07°. There exists a H-bonded S11(6) graph set in the 5-nitrosalicylate, this feature resembles that occurred in the salicylic acid [31], and in the previously archived salt with 5-nsa- [32].

EP

As anticipated the O-O separation is in the lower border of the reported values [2.489-2.509 Å] [32], but it is slightly shortened compared with the nonproton

AC C

transfer compounds (2.547-2.604 Å, average: 2.588 Å). Compared with the known torsion angles (175.4-180°) within the published salts of 5-nsa- [32], the torsion angle [C20-C21-N5-O5, -178.24°] concerning the 5-NO2 also varies little. At every NH+ of the H2L3 there was bonded a L2 via the N-H···N H-bond

between the NH+ of the H2L3 and the N at the L2 with N-N distance of 2.822(4) Å to form a tricomponent adduct. At every L2 of the tricomponent adduct there each attached a 5-nitrosalicylate by the bifurcated N-H···O H-bonds between the NH and both O of the COO- with N-O distances of 2.709(4)-3.269(5) Å, and CH-O association between the aromatic CH of the L2 and the COO- with C-O distance of

ACCEPTED MANUSCRIPT 3.408 Å to form a five-component aggregate with XIX R12(4), and XX R21(6) loops. The fivecomponent aggregates were linked into 1D chain by three CH-O associations. One O of the NO2 as a double acceptor accepted two CH-O associations: one from the N-CH-N of the H2L3 with C-O separation of 3.283 Å, the other from the aryl CH of

RI PT

the L2 with C-O distance of 3.224 Å. The other O of the NO2 formed the CH-O association from the aryl CH of the H2L3 with C-O distance of 3.207 Å.

The discrete 1D parallel chains formed a sheet extending at the direction that made an angle of ca. 60° with the ac plane (Fig. 10), but there were not established

SC

any bonding interactions among these chains. There were XXI R32(9), XXII R22(12), and XXIII R66(38) synthons between two fivecomponent aggregates. Within the

M AN U

crystal structure, neighboring sheets are linked through additional intersheet CH-O associations arising from the COO- and the N-CH-N of the L2 with C-O separation of 3.272 Å, CH2-O association between the CH2 spacer at the H2L3 and the phenol unit at the anion with C-O distance of 3.333 Å, and π-π stacking between the benzimidazole ring of the H2L3 and the phenyl ring of the 5-nsa- with Cg-Cg distance

TE D

of 3.369 Å to give an overall 3D layer network. In this regard, the neighboring sheets were moved some distances from each other along the extending directions. IR absorption spectrum analysis of 1-5

EP

The O-H or N-H stretching frequencies were found at approximately 3701-3333 cm-1 as strong and broad bands in the IR spectra of the five compounds. The medium

AC C

intensity bands occurred at 1500-1630 cm-1 and 600-750 cm-1 are attributed to the aromatic ring stretching and bending, respectively. IR spectroscopy is very useful for the diagnosis of H-transfer compounds [33], for in the H-transfer compounds 2-5, the most noticeable feature in the IR spectrum are the presence of strong asymmetrical (1575-1609 cm-1) and symmetrical (1379-1400 cm-1) COO- stretching frequencies [34], respectively. Salts 3, and 4 exhibit additional strong IR peaks for COOH groups, the bands in 5 at 1526 and 1318 cm-1 were attributed to the νas(NO2), and νs(NO2), respectively [35].

ACCEPTED MANUSCRIPT Conclusion Five imidazole derivatives based organic salts with different organic anions have been synthesized and characterized by XRD analysis. The structure analysis confirms that the N units in the imidazole are protonated, which made novel contributions to

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the extensive study into the foundation of acid-imidazole synthons in organic salts. Robust H-bonds together with other weak associations led to the final production of distinct 3D supramolecular networks. Although the acids utilized in this text were different from each other, the salt structures display some certain common structural

SC

features: in all of the crystal packing, the building blocks of 1-5 are self-assembled via N-H···O H-bonds, salts 2-5 possess the additional O-H···O H-bonds, compound 1

M AN U

had the N-H···S H-bonds. The weak CH-O/CH2-O/CH3-O, CH-S, CH-π, NH-π, and π-π associations also become prominent in the construction of the final supramolecular networks.

For the N atoms decrease the electron density at the neighboring C-H protons inductively and raise the donor capability of the C-H protons, thus the CH-O bonds

TE D

from the N-CH-N of the imidazole were established in all of the salts. It is worthy to note that the intersheet CH-O bonds from the N-CH-N of the imidazole were found in all of the salts except 1, the reason may be that the imidazolium in 1 were surrounded

EP

by seven O atoms (all of the CH on the cations generate at least one CH-O hydrogen bond with O atoms within the sheet layer), while the imidazole rings at 2-5 were not coplanar with the plane defined by the anion, and this twisting of the cations leads the

AC C

Hs on the N-CH-N to direct slightly or severely away from a given layer. All 3D structures contain the 1D sub-chain and 2D sub-sheet, from an inspection of the role exhibited by each set of interactions, it seems that the intra- and interchain noncovalent bonds played equal importance in space expansion. In this study, an intricate set of supramolecular synthons with small and large sized ring graph sets were observed including R12(4), R12(7), R21(5), R21(6), R22(4), R22(7), R22(8), R22(10), R22(12), R22(11), R32(9), R32(10), R33(9), R42(9), R42(10), R44(21), and R66(38), but not all of them occurred regularly, as most of them were observed only in some structures. The five structures presented here further disclose

ACCEPTED MANUSCRIPT that the imidazole is a good building segment to be embodied into organic salts so as to architecture diversiform and stable H-bonded structures, and we will further explore more multicomponent cocrystals/molecular salts bearing imidazole and the acids building unit to further understand the supramolecular chemistry of

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imidazole-acid.

Acknowledgement

This research was supported by Zhejiang Provincial Natural Science Foundation

SC

of China under Grant No. LY14B010006, and the Open Fund of Zhejiang Provincial

M AN U

Top Key Discipline of Forestry Engineering under Grant No. 2014LYGCZ017.

Supporting Information Available: Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic data center, CCDC Nos. CCDC 955587for 1, 956460 for 2, 963212 for 3, 959387 for 4, and 1521032 for 5. Copies of this information may be obtained free of charge from the or

Email:

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+44(1223)336-033

[email protected]

or

www:

http://www.ccdc.cam.ac.uk.

EP

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AC C

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ACCEPTED MANUSCRIPT Molecular

Building

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3,3-Bis(2-imidazolyl)propionic

Based

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Acid

the

Protonation/Deprotonation

(HBIP):

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Hydrogen bonded supramolecular network in organic acid–base salts: Crystal of

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2,2,4-Trimethyl-2,3-dihydro-1H-1,5-benzodiazepin-5-ium

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Acta Cryst. E63 (2007) o4909.

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H.

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Barnes,

J.

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2-Methyl-1,2,3-propanetricarboxylic 1,2,3-Propanetricarboxylate

Barnes, Acid,

Hemihydrate

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1,2,3,4-Butanetetracarboxylate Monohydrate, Acta Cryst. C52 (1996) 731. V.

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Supramolecular Synthon Using N-Methylaniline. The Crystal Structure of the 1 : 1 Adduct of N-Methylaniline with 5-Nitrofuran-2-carboxylic Acid, Aust. J. Chem. 51 (1998) 867; (b) G. Smith, J. M. White, Short Communication: Molecular Cocrystals

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of Carboxylic Acids: the Preparation of the 1: 1 Proton-Transfer Compounds of Creatinine with a Series of Aromatic Acids and the Crystal Structure of that with Pyrazine-2,3-dicarboxylic Acid, Aust. J. Chem. 54 (2001) 97.

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[34] D. H. Williams, I. Fleming, (1995) Spectroscopic Methods in Organic Chemistry, 5th ed., McGraw-hill, London. [35] M. Lazzarrotto, E. E. Castellano, F. F. Nachtigall, Morpholinium 2,4-dinitrophenolate Aqua Salt and Ethylenediammonium 2,4-dinitrophenolate Aqua Salt, J. Chem. Crystallogr. 37 (2007) 699.

ACCEPTED MANUSCRIPT Figure captions

Fig. 1 The structure of 1, showing the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

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Fig. 2 2D corrugated sheet structure structure of 1 extending parallel to the bc plane.

Fig. 3 The structure of 2, showing the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

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Fig. 4 2D grid sheet structure of 2 extending parallel to the bc plane.

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Fig. 5 The structure of 3, showing the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Fig. 6 2D sheet structure of 3 extending parallel to the ab plane.

Fig. 7 The structure of 4, showing the atom-numbering scheme. Displacement

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ellipsoids were drawn at the 30% probability level.

Fig. 8 2D sheet structure of 4 extending at the direction that made an angle of ca. 60° with the bc plane.

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Fig. 9 The structure of 5, showing the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

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Fig. 10 2D sheet structure of 5 extending at the direction that made an angle ca. 60° with the ac plane.

ACCEPTED MANUSCRIPT Covering information sheet Journal name: JOURNAL OF MOLECULAR STRUCTURE Title: Structure of Five Molecular Salts Assembled from Noncovalent between

Organic

Acids,

Imidazole,

and

Corresponding author: Huan Zhang

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1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole

Benzimidazole,

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Associations

Address: ZheJiang A & F University, Lin’an, Zhejiang Province, 311300, P. R. China, Tel & fax: +86-571-6374-6755.

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E-mail: [email protected]

Figures : 10

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Tables: 3

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Numbers of pages: 24pp

ACCEPTED MANUSCRIPT Table 1. Summary of X-ray crystallographic data for complexes 1 - 5.

θ range, deg Limiting indices Reflections collected Reflections independent (Rint)

4 C15H16N2O8 352.30 298(2) 0.71073 Monoclinic P2/n 5.1000(5) 10.6779(9) 13.8204(12) 90 90.1410(10) 90 752.62(12) 2 1.555

5 C44H36N10O10 864.83 293(2) 0.71073 Triclinic P-1 8.8800(8) 9.2656(8) 12.3474(11) 93.7320(10) 101.566(2) 90.4920(10) 992.94(15) 1 1.446

0.232

0.114

0.119

0.128

0.106

640 0.41 x 0.32 x 0.29 2.70 - 25.02 -10 ≤ h ≤ 10 -14 ≤ k ≤ 13 -15 ≤ l ≤ 16 7548 4325 (0.0325)

464 0.37 x 0.25 x 0.23 2.69 - 25.00 -10 ≤ h ≤ 10 -13 ≤ k ≤ 13 -11 ≤ l ≤ 11 4725 1738(0.0734)

528 0.38 x 0.11 x 0.09 3.03 - 25.02 -4 ≤ h ≤ 4 -16 ≤ k ≤ 16 -18 ≤ l ≤ 24 5781 1998 (0.0803)

368 0.45 x 0.38 x 0.35 2.95 - 25.01 -6 ≤ h ≤ 6 -10 ≤ k ≤ 12 -16 ≤ l ≤ 16 3652 1327 (0.0349)

450 0.41 x 0.33 x 0.24 2.60 - 25.02 -10 ≤ h ≤ 10 -10 ≤ k ≤ 11 -14 ≤ l ≤14 5695 3503 (0.0440)

1.192 0.0981, 0.2655 0.1343, 0.3142

Largest diff. peak and hole, e.Å-3

1.023, -0.595

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Goodness-of-fit on F2 R indices [I > 2σI] R indices (all data)

1.076 0.0469, 0.1089 0.0645, 0.1193

0.929 0.0540, 0.1372 0.1006, 0.1545

1.020 0.0378, 0.0913 0.0560, 0.1042

1.019 0.0659, 0.1358 0.1552, 0.1928

0.187, -0.184

0.198, -0.245

0.216, -0.220

0.289, -0.280

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3 C11H12N2O5 252.23 298(2) 0.71073 Orthorhombic P2(1)2(1)2(1) 3.8062(3) 14.2168(17) 20.9393(18) 90 90 90 1133.07(19) 4 1.479

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2 C10H10N2O4 222.20 298(2) 0.71073 Orthorhombic Pna2(1) 8.8629(5) 11.3747(8) 10.1149(6) 90 90 90 1019.71(11) 4 1.447

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Absorption coefficient, mm-1 F(000) Crystal size, mm3

1 C13H20N2O4S 300.37 298(2) 0.71073 Monoclinic P2(1) 9.0257(6) 12.2261(12) 13.5078(14) 90 90.7830(10) 90 1490.4(2) 4 1.339

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Formula Fw T, K Wavelength, Å Crystal system space group a, Å b, Å c, Å α, deg. β, deg. γ, deg. V, Å3 Z Dcalcd, Mg/m3

ACCEPTED MANUSCRIPT Table 2 Selected bond lengths [Å] and angles [°] for 1 - 5

1.381(14) 1.323(15) 1.274(14) 1.359(14) 1.459(6) 1.185(14) 1.447(8) 1.265(15) 107.5(9) 105.6(10) 113.0(5) 110.6(6) 113.0(5) 111.2(11)

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1.302(4) 1.295(5) 1.248(4) 1.364(4) 108.2(3) 109.5(3)

N(1)-C(3) N(2)-C(2) N(3)-C(4) N(4)-C(5) O(2)-S(1) O(4)-C(9) O(6)-S(2) O(8)-C(19) C(1)-N(2)-C(2) C(4)-N(4)-C(5) O(1)-S(1)-O(2) O(7)-S(2)-O(5) O(5)-S(2)-O(6) N(3)-C(4)-N(4)

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1.270(13) 1.308(13) 1.272(16) 1.294(15) 1.429(7) 1.457(8) 1.442(7) 1.429(9) 107.9(9) 109.3(11) 113.7(5) 109.9(4) 113.0(6) 109.3(9)

N(1)-C(3) N(2)-C(2) O(2)-C(4) O(4)-C(9) C(1)-N(2)-C(2) O(1)-C(4)-O(2)

1.341(5) 1.342(5) 1.253(4) 1.358(3) 108.2(3) 124.6(3)

N(1)-C(3) N(2)-C(2) O(2)-C(4) O(4)-C(5) C(1)-N(2)-C(2) O(1)-C(4)-O(2)

1.346(5) 1.344(4) 1.262(4) 1.208(4) 109.3(3) 123.0(4)

1.317(2) 1.226(2) 1.294(2) 108.55(18) 126.11(17)

N(1)-C(2) O(2)-C(5) O(4)-C(8) N(1)#1-C(1)-N(1) O(4)-C(8)-O(3)

1.384(3) 1.272(2) 1.229(2) 110.3(3) 123.53(17)

1.350(5) 1.527(6) 1.292(5) 1.319(4) 1.321(5) 1.450(5) 1.268(5) 105.8(3)

N(1)-C(4) N(1)-C(1') N(2)-C(3) N(3)-C(11) N(4)-C(10) O(1)-C(16) O(3)-C(18) C(2)-N(1)-C(1)

1.387(5) 1.530(7) 1.377(4) 1.382(5) 1.394(5) 1.248(5) 1.333(5) 125.5(5)

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1.311(5) 1.300(5) 1.225(4) 1.314(5) 108.8(4) 108.0(4) 123.3(4)

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1 N(1)-C(1) N(2)-C(1) N(3)-C(6) N(4)-C(4) O(1)-S(1) O(3)-S(1) O(5)-S(2) O(7)-S(2) C(1)-N(1)-C(3) C(6)-N(3)-C(4) O(1)-S(1)-O(3) O(3)-S(1)-O(2) O(7)-S(2)-O(6) N(1)-C(1)-N(2) 2 N(1)-C(1) N(2)-C(1) O(1)-C(4) O(3)-C(7) C(1)-N(1)-C(3) N(2)-C(1)-N(1) 3 N(1)-C(1) N(2)-C(1) O(1)-C(4) O(3)-C(5) C(1)-N(1)-C(3) N(2)-C(1)-N(1) O(4)-C(5)-O(3) 4 N(1)-C(1) O(1)-C(5) O(3)-C(8) C(1)-N(1)-C(2) O(1)-C(5)-O(2) 5 N(1)-C(2) N(1)-C(1) N(2)-C(2) N(3)-C(9) N(4)-C(9) N(5)-C(21) O(2)-C(16) C(2)-N(1)-C(4)

ACCEPTED MANUSCRIPT C(4)-N(1)-C(1) C(4)-N(1)-C(1') C(2)-N(2)-C(3) C(9)-N(4)-C(10) N(3)-C(9)-N(4)

123.6(4) 125.4(5) 105.7(3) 107.5(3) 111.2(4)

C(2)-N(1)-C(1') C(1)-N(1)-C(1') C(9)-N(3)-C(11) N(2)-C(2)-N(1) O(1)-C(16)-O(2)

119.3(6) 47.5(4) 108.5(3) 113.4(4) 124.7(4)

Symmetry transformations used to generate equivalent atoms for 4: #1 -x+3/2, y,

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-z+3/2.

ACCEPTED MANUSCRIPT Table 3 Hydrogen bond distances and angles in studied structures 1 - 5. d(D···A) [Å]

<(DHA)[°]

0.86 0.86 0.86 0.86 0.86 0.86 0.86 0.86

2.97 1.99 2.49 2.06 2.53 2.02 2.97 1.91

3.828(10) 2.811(12) 3.002(12) 2.855(13) 3.082(13) 2.793(11) 3.806(8) 2.747(10)

175.7 158.0 119.0 152.8 122.6 149.2 164.0 163.1

0.82 0.82 0.86 0.86

1.91 1.84 1.95 2.01

2.661(3) 2.660(3) 2.758(4) 2.794(4)

151.7 175.4 157.0 151.6

2.312(5) 2.312(5) 2.803(8) 2.554(3) 2.672(4) 2.780(4)

119.5 168.5 168.5 168.5 173.7 176.8

1.77 1.47 1.96 1.75 1.81 1.92

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0.85 0.85 0.85 0.82 0.86 0.86

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d(H···A) [Å]

0.82 0.82 0.86

1.82 1.64 1.91

2.6280(18) 2.439(3) 2.768(2)

169.1 164.1 174.5

0.86 0.86 0.86 0.82

1.97 1.87 2.59 1.73

2.822(4) 2.709(4) 3.269(5) 2.470(4)

167.9 163.5 136.9 148.8

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1 N(4)-H(4)···S(1)#1 N(4)-H(4)···O(3)#1 N(3)-H(3)···O(2)#2 N(3)-H(3)···O(5)#3 N(2)-H(2)···O(5)#4 N(2)-H(2)···O(2)#5 N(1)-H(1)···S(2)#1 N(1)-H(1)···O(6)#1 2 O(4)-H(4)···O(1)#1 O(3)-H(3)···O(1)#2 N(2)-H(2)···O(2)#3 N(1)-H(1)···O(2)#4 3 O(5)-H(5B)···O(5)#1 O(5)-H(5D)···O(5)#2 O(5)-H(5C)···O(1)#3 O(3)-H(3)···O(2)#4 N(2)-H(2)···O(1)#5 N(1)-H(1)···O(2) 4 O(3)-H(3)···O(4)#3 O(2)-H(2)···O(2)#4 N(1)-H(1)···O(1)#5 5 N(2)-H(2)···N(4) N(3)-H(3)···O(1)#2 N(3)-H(3)···O(2)#2 O(3)-H(3A)···O(2)

d(D-H) [Å]

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D-H···A

Symmetry transformations used to generate equivalent atoms for 1: #1 x+1, y, z; #2 -x, y-1/2, -z+1; #3 -x, y-1/2, -z+2; #4 -x, y+1/2, -z+2; #5 -x, y+1/2, -z+1. Symmetry transformations used to generate equivalent atoms for 2: #1 -x+1/2, y-1/2, z+1/2; #2 -x+1, -y+1, z+1/2; #3 x, y-1, z; #4 -x+1, -y+1, z-1/2. Symmetry transformations used to generate equivalent atoms for 3: #1 x-1/2, -y+1/2, -z+1; #2 x+1/2, -y+1/2, -z+1; #3 -x+3/2, -y+1, z+1/2; #4 -x+2, y-1/2, -z+1/2; #5 -x+1, y-1/2, -z+1/2. Symmetry transformations used to generate equivalent atoms for 4: #3 -x+1/2, y, -z+3/2; #4 -x+1, -y, -z+1; #5 x+1, y+1, z. Symmetry transformations used to generate equivalent atoms

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for 5: #2 -x+1, -y+1, -z+1.

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Highlights

Five salts have been prepared and characterized. Noncovalent interactions have been ascertained.

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H-bonds are the driving forces forming the OH···imidazole synthon.

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Other weak interactions also play important role in structure expansion.